JP5930243B2 - Radiation curable ink composition and ink jet recording method - Google Patents

Description

  The present invention relates to a radiation curable ink composition, and an ink jet recording method and a recorded matter using the same.

  In recent years, development of radiation-curable inks that are cured by ultraviolet rays, electron beams, or other radiation has been promoted. Such a radiation curable ink is capable of quick-drying and recording that prevents ink bleeding when recording on non-absorbing media that does not absorb or hardly absorbs ink such as plastic, glass, and coated paper. Can do. Such radiation curable ink is composed of a polymerizable monomer, a polymerization initiator, a pigment and other additives.

  Incidentally, a recorded matter in which an image is formed on a flexible recording medium such as a polyethylene terephthalate resin or a vinyl chloride resin may be affixed to an article having a curved surface such as a vehicle body. In such an application, since the recorded matter is usually stretched and attached to an article, the image formed on the recording medium does not cause cracking or peeling even when stretched, and the elongation is 100% or more. It is desirable to have

  Conventional radiation curable inks use polymerizable monomers such as long-chain alkyl acrylate, phenoxyethyl acrylate, and ethylene oxide adducts of phenoxyethyl acrylate to record flexible images having an elongation of 100% or more. (For example, see Patent Documents 1 to 3). These compounds were selected for the purpose of simply setting the glass transition temperature when forming a homopolymer to room temperature or lower.

Japanese Patent Laid-Open No. 2006-199924 JP 2007-131754 A JP 2008-7687 A

  However, the image recorded using the radiation curable ink as described above cannot be said to have sufficient adhesion to the recording medium, and there is a problem that the image is peeled off from the recording medium. Further, since the toughness of the recorded image was insufficient, the abrasion resistance was not excellent. Further, an image recorded using a conventional radiation curable ink may not be sufficiently flexible in the applications as described above, and may crack and / or peel off.

  Some aspects of the present invention provide a radiation curable ink that is excellent in storage stability and has excellent flexibility, abrasion resistance, and adhesion to a recording medium in a recorded image by solving the above-described problems. A composition is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the radiation curable ink composition according to the present invention is:
(A) 5 to 15% by mass of N-vinylcaprolactam in the reaction component;
(B) a polyfunctional acrylate having an alicyclic structure of 1% by mass to 20% by mass in the reaction component;
(C) phenoxyethyl acrylate,
It is characterized by containing.

  According to the radiation curable ink composition of Application Example 1, the storage stability is excellent, and the recorded image has excellent flexibility, abrasion resistance, and adhesion to the recording medium.

[Application Example 2]
In application example 1,
The polyfunctional acrylate having the (B) alicyclic structure may be dimethylol tricyclodecane diacrylate.

[Application Example 3]
In application example 1 or application example 2,
Furthermore, the monofunctional acrylate which has 35 mass% or more and 65 mass% or less of alicyclic structure can be contained in (D) reaction component.

[Application Example 4]
In application example 3,
The (D) monofunctional acrylate having an alicyclic structure may be at least one selected from dicyclopentenyl acrylate, dicyclopentanyl acrylate, and dicyclopentenyloxyethyl acrylate.

[Application Example 5]
In any one of Application Examples 1 to 4,
Furthermore, (E) amino acrylate can be contained.

[Application Example 6]
In any one of Application Examples 1 to 5,
The viscosity at a measurement temperature of 20 ° C. may be from 10 mPa · s to 40 mPa · s, and the surface tension at a measurement temperature of 20 ° C. may be from 20 mN / m to 30 mN / m.

[Application Example 7]
One aspect of the inkjet recording method according to the present invention is:
(A) discharging the radiation curable ink composition according to any one of Application Examples 1 to 6 onto a recording medium;
(B) irradiating the discharged radiation curable ink composition with actinic radiation having an emission peak wavelength in a range of 350 nm to 400 nm from an actinic radiation source;
It is characterized by including.

[Application Example 8]
The recorded matter according to the present invention is:
It is recorded by the ink jet recording method described in Application Example 7.

1 is a perspective view of an ink jet recording apparatus that can be used in an ink jet recording method according to the present embodiment. The front view of the active radiation irradiation apparatus shown in FIG. FIG. 3 is an AA arrow view of FIG. 2.

  Hereinafter, preferred embodiments of the present invention will be described. The embodiment described below describes an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention. In the following description, the materials (A) to (F) may be abbreviated as components (A) to (F), respectively.

1. Radiation curable ink composition A radiation curable ink composition according to an embodiment of the present invention includes (A) 5% by mass or more and 15% by mass or less of N-vinylcaprolactam in the reaction component, and (B) in the reaction component. 1 to 20% by mass of a polyfunctional acrylate having an alicyclic structure and (C) phenoxyethyl acrylate. In the present invention, the “reaction component” refers to a polymerizable monomer used to form a polymer, and does not include other additives such as pigments, dispersants, photopolymerization initiators, and slip agents. . In the present invention, “image” indicates a print pattern formed from a group of dots, and includes text printing and solid printing.

  Hereinafter, each component used for this Embodiment is demonstrated in detail.

1.1. (A) N-vinylcaprolactam The radiation curable ink composition according to the present embodiment contains (A) N-vinylcaprolactam in the reaction component. The radiation curable ink composition according to this embodiment can improve the adhesion between the recording medium and the image recorded thereon by containing (A) N-vinylcaprolactam in the reaction component. . Further, (A) N-vinylcaprolactam has good curability, has good dilutability with respect to other polymerizable monomers, and (B) a polyfunctional acrylate having an alicyclic structure and (C) The function of phenoxyethyl acrylate is not inhibited.

  (A) The content of N-vinylcaprolactam is 5% by mass or more and 15% by mass or less, preferably 10% by mass or more and 15% by mass or less, when the total mass of the reaction components is 100% by mass. When the content of (A) N-vinylcaprolactam in the reaction component is less than 5% by mass, the adhesion between the recording medium and the image recorded thereon may not be excellent. On the other hand, if it exceeds 15% by mass, the storage stability of the radiation curable ink composition may not be excellent, and may not be suitable for use as a product.

1.2. (B) Polyfunctional acrylate having alicyclic structure The radiation curable ink composition according to the present embodiment contains (B) a polyfunctional acrylate having an alicyclic structure in the reaction component. Such a polyfunctional acrylate usually functions as a crosslinking agent, but the polyfunctional acrylate has a bulky structure such as an alicyclic structure, so that not only the curing time by photopolymerization can be shortened but also the polymer formed The strength of can be improved. That is, the radiation curable ink composition according to the present embodiment contains (B) a polyfunctional acrylate having an alicyclic structure in the reaction component, thereby providing toughness to an image recorded on a recording medium. This can improve the abrasion resistance. In addition, (B) the polyfunctional acrylate having an alicyclic structure has good dilutability with respect to other polymerizable monomers, and inhibits the functions of (A) N-vinylcaprolactam and (C) phenoxyethyl acrylate. There is no.

  (B) Examples of the polyfunctional acrylate having an alicyclic structure include dimethylol tricyclodecane diacrylate, 1,3-adamantanediol diacrylate, and the like. These polymerizable monomers can be used alone or in combination of two or more.

  (B) The content of the polyfunctional acrylate having an alicyclic structure is 1% by mass or more and 20% by mass or less, preferably 10% by mass or more and 20% by mass or less when the total mass of the reaction components is 100% by mass. It is as follows. When the content of the (B) polyfunctional acrylate having an alicyclic structure in the reaction component is less than 1% by mass, the abrasion resistance of the image recorded on the recording medium tends to deteriorate. On the other hand, if it exceeds 20% by mass, the flexibility of the image recorded on the recording medium tends to be inferior, and cracks are likely to occur in the image recorded on the recording medium. In addition, since the viscosity of the radiation curable composition is increased, there is a tendency to easily cause clogging or the like in the nozzles of the ink jet printer.

1.3. (C) Phenoxyethyl acrylate The radiation curable ink composition according to the present embodiment contains (C) phenoxyethyl acrylate in the reaction component. The radiation curable ink composition according to this embodiment can improve flexibility and stretch durability of an image recorded on a recording medium by containing (C) phenoxyethyl acrylate in the reaction component. . Further, phenoxyethyl acrylate has a good curability and a good dilutability with respect to other polymerizable monomers, and thus has a feature that it is very easy to use.

  (C) The content of phenoxyethyl acrylate is preferably 5% by mass or more and 65% by mass or less, more preferably 10% by mass or more and 50% by mass or less, when the total mass of the reaction components is 100% by mass. . When the content of (C) phenoxyethyl acrylate in the reaction component is less than 5% by mass, the flexibility of the image recorded on the recording medium may not be excellent. On the other hand, if it exceeds 65% by mass, the storage stability of the radiation curable ink composition may not be excellent, and thus it is not suitable for use as a product.

1.4. (D) Monofunctional acrylate having alicyclic structure The radiation curable ink composition according to the present embodiment may further contain (D) a monofunctional acrylate having an alicyclic structure in the reaction component. The radiation curable ink composition according to the present embodiment contains (D) a monofunctional acrylate having an alicyclic structure in the reaction component, so that the viscosity of the radiation curable ink composition is suitable for an ink jet recording system. To a low value (20 ° C./10 mPa · s or more and 40 mPa · s or less). This is because monofunctional acrylates generally have a low viscosity. Further, by having a bulky alicyclic structure, it is possible to impart toughness to an image recorded on a recording medium, thereby improving the abrasion resistance.

  (D) Examples of monofunctional acrylates having an alicyclic structure include dicyclopentenyloxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, trimethylolpropane formal monoacrylate, adamantyl acrylate, Examples include oxetane acrylate and 3,3,5-trimethylcyclohexane acrylate. These polymerizable monomers can be used alone or in combination of two or more.

(D) The content of the monofunctional acrylate having an alicyclic structure is preferably 35% by mass or more and 65% by mass or less when the total mass of the reaction components is 100% by mass. When the content of the (D) monofunctional acrylate having an alicyclic structure in the reaction component is less than 35% by mass, the abrasion resistance of the image recorded on the recording medium tends to be low. On the other hand, if it exceeds 65% by mass, the flexibility of the image recorded on the recording medium tends to be poor and cracks are likely to occur in the image recorded on the recording medium.

1.5. (E) Aminoacrylate The radiation curable ink composition according to the present embodiment may further contain (E) aminoacrylate in the reaction component. The radiation curable ink composition according to the present embodiment can promote the copolymerization reaction by containing (E) amino acrylate in the reaction component.

  The content of (E) amino acrylate is preferably 1% by mass or more and 5% by mass or less when the total mass of the reaction components is 100% by mass. When the content of (E) amino acrylate in the reaction component is less than 1% by mass, the copolymerization reaction does not proceed smoothly and the curability of the image recorded on the recording medium may be insufficient. On the other hand, if it exceeds 5% by mass, the effect of promoting the copolymerization reaction is not improved, and excessive addition is not preferable.

1.6. (F) Photopolymerization initiator The radiation-curable ink composition according to the present embodiment may further contain (F) a photopolymerization initiator in addition to the reaction components described above. The photopolymerization initiator is a general term for compounds having a function of initiating a copolymerization reaction of the above-described reaction components by irradiating the radiation curable ink composition discharged onto the recording medium with actinic radiation.

  (F) Examples of photopolymerization initiators include known photopolymerization initiators such as alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and thioxanthone photopolymerization initiators. Agents. Among these, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide having excellent compatibility with the above-mentioned reaction components, bis (2,4,6-trimethylbenzoyl) -phenylphosphine having a wide range of light absorption characteristics A molecular cleavage type such as fin oxide and a hydrogen abstraction type such as diethylthioxanthone are preferred. The reason why acylphosphine oxide-based photopolymerization initiators are preferable is that the structure of the chromophore changes greatly before and after photocleavage, so the change in absorption is large, and a short wavelength of absorption called photobleaching (photobleaching) is observed. Because it is. Moreover, it is because yellowing hardly occurs despite the absorption ranging from the UV to the VL region, and is excellent in internal curing. For this reason, it is particularly preferable for a transparent thick film or a pigmented coating film having a large hiding power. The reason why the thioxanthone photopolymerization initiator is preferable is that it reacts with oxygen remaining in the reaction system after photocleavage to lower the concentration of oxygen in the system. Since the degree of radical polymerization inhibition can be reduced as much as the oxygen concentration decreases, the surface curability can be improved. Further, it is particularly preferable to use an acyl phosphonic photopolymerization initiator and a thioxanthone photopolymerization initiator in combination. These photopolymerization initiators can be used singly or in combination of two or more, and each characteristic can be maximized.

  (F) Content of a photoinitiator becomes like this. Preferably it is 1 to 20 mass parts with respect to 100 mass parts of reaction components, More preferably, it is 5 to 15 mass parts. When the amount is less than 1 part by mass relative to 100 parts by mass of the reaction, the function of the photopolymerization initiator may not be exhibited, and the curability of the image recorded on the recording medium may be insufficient. On the other hand, even if it exceeds 20 parts by mass, the effect of initiating the above-described copolymerization reaction of the reaction components is not seen, and it is not preferable because it is excessively added.

1.7. Other Additives The radiation curable ink composition according to the present embodiment can contain additives such as pigments, dispersants, slip agents, photosensitizers, polymerization inhibitors, and the like as necessary.

  The radiation curable ink composition according to this embodiment can function as a so-called clear ink as it is, but may further contain a pigment. Although it does not restrict | limit especially as a pigment which can be used in this Embodiment, An inorganic pigment and an organic pigment are mentioned. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. On the other hand, organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinofullerone pigments, etc.) Nitro pigments, nitroso pigments, aniline black, and the like can be used.

  Among specific examples of pigments that can be used in the present embodiment, carbon black includes C.I. I. Pigment black 7, for example, No. available from Mitsubishi Chemical Corporation. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. Raven5750, 5250, 5000, 3500, 1255, 700, etc. available from Columbia Chemical Company 2200B, etc. Also, Regal400R, 330R, 660R, MoguL, available from Cabot 700, Monarch 800, 880, 900, 1000, 1100, 1300, 1400, etc. are further available from Degussa, such as ColorBlack FW1, FW2, FW2V, FW18, FW200, ColorBlackS150, S160. , S170, Printex35, U, V, 140U, Special Black6, 5, 4A, 4 and the like.

  Examples of pigments that can be used when the radiation curable ink composition according to the present embodiment is yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 180, 185, 213 and the like.

  Examples of pigments that can be used when the radiation curable ink composition according to the present embodiment is magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 168, 184, 202, 209, C.I. I. Pigment violet 19 and the like.

  Examples of pigments that can be used when the radiation curable ink composition according to the present embodiment is cyan ink include C.I. I. Pigment blue 1, 2, 3, 15: 3, 15: 4, 16, 22, 60, and the like.

  Examples of pigments that can be used when the radiation curable ink composition according to the present embodiment is a green ink include C.I. I. Pigment green 7, 8, 36, and the like.

  Examples of pigments that can be used when the radiation curable ink composition according to this embodiment is an orange ink include C.I. I. Pigment orange 51, 66 and the like.

  Examples of pigments that can be used when the radiation curable ink composition according to this embodiment is white ink include basic lead carbonate, zinc oxide, titanium oxide, and strontium titanate.

  The average particle diameter of the pigment that can be used in the present embodiment is preferably in the range of 10 nm to 200 nm, more preferably in the range of 50 nm to 150 nm.

  The amount of the pigment that can be added to the radiation curable ink composition according to the present embodiment is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 100 parts by mass of the reaction component. Part by mass to 15 parts by mass.

  In the radiation curable ink composition according to the present embodiment, a dispersant may be added for the purpose of enhancing the dispersibility of the pigment. Dispersants that can be used in the present embodiment include Solsperse 3000, 5000, 9000, 12000, 13240, 17000, 24000, 26000, 28000, 36000 (above, manufactured by Lubrizol), DISCOL N-503, N-506. , N-509, N-512, N-515, N-518, N-520 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

  The radiation curable ink composition according to this embodiment may contain a slip agent. The slip agent that can be used in the present embodiment is preferably a silicone-based surfactant, more preferably a polyester-modified silicone or a polyether-modified silicone. Specifically, examples of the polyester-modified silicone include BYK-347, 348, BYK-UV3500, 3510, 3530 (above, manufactured by BYK Chemie Japan Co., Ltd.), and the polyether-modified silicone includes BYK. -3570 (made by Big Chemie Japan Co., Ltd.) and the like.

  A photosensitizer may be added to the radiation curable ink composition according to the present embodiment. Photosensitizers usable in the present embodiment include amine compounds (aliphatic amines, amines containing aromatic groups, piperidine, reaction products of epoxy resins and amines, triethanolamine triacrylate, etc.), urea compounds (Allylthiourea, o-tolylthiourea, etc.), sulfur compounds (sodium diethyldithiophosphate, soluble salts of aromatic sulfinic acid, etc.), nitrile compounds (N, N-diethyl-p-aminobenzonitrile, etc.), phosphorus compounds ( Tri-n-butylphosphine, sodium diethyldithiophosphide, etc.), nitrogen compounds (Michler ketone, N-nitrisohydroxylamine derivative, oxazolidine compound, tetrahydro-1,3-oxazine compound, formaldehyde or a condensate of acetaldehyde and diamine) ), Chlorine compounds (carbon tetrachloride, hexachloroethane, etc.) and the like.

  A polymerization inhibitor may be added to the radiation curable ink composition according to the present embodiment. Examples of the polymerization inhibitor that can be used in the present embodiment include hydroquinone, benzoquinone, p-methoxyphenol, and the like.

1.8. Physical Properties The viscosity at 20 ° C. of the radiation curable ink composition according to the present embodiment is preferably 10 to 40 mPa · s, more preferably 15 to 25 mPa · s. When the viscosity at 20 ° C. of the radiation curable ink composition is within the above range, an appropriate amount of the radiation curable ink composition is ejected from the nozzle, and the flight bending and scattering of the radiation curable ink composition can be further reduced. Therefore, it can be suitably used for an ink jet recording apparatus. The viscosity was measured by using a viscoelasticity tester MCR-300 (manufactured by Pysica), increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200 hours.

The surface tension at 20 ° C. of the radiation curable ink composition according to the present embodiment is preferably 20 mN / m or more and 30 mN / m or less. When the surface tension at 20 ° C. of the radiation curable ink composition is within the above range, the radiation curable ink composition is hardly wetted by the liquid-repellent treated nozzle. Accordingly, an appropriate amount of the radiation curable ink composition is ejected from the nozzle, and the flight bending and scattering of the radiation curable ink composition can be further reduced, so that it can be suitably used for an ink jet recording apparatus. The surface tension was measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) to confirm the surface tension when the platinum plate was wetted with ink in an environment of 20 ° C.

2. Inkjet Recording Method An inkjet recording method according to an embodiment of the present invention includes: (a) a step of discharging the radiation curable ink composition described above onto a recording medium; and (b) a discharged radiation curable ink composition. On the other hand, the step of irradiating actinic radiation having an emission peak wavelength in a range of 350 nm or more and 400 nm or less from an actinic radiation light source is included.

  Hereinafter, the ink jet recording method according to the present embodiment will be described for each step.

2.1. Step (a)
This step is a step of discharging the radiation curable ink composition described above onto a recording medium.

  Since the radiation curable ink composition is as described above, detailed description thereof is omitted.

  The recording medium is not particularly limited, and examples thereof include plastics such as polyvinyl chloride, polyethylene terephthalate, polypropylene, polyethylene, and polycarbonate, those whose surfaces are processed, glass, coated paper, and the like.

  As means for discharging the radiation curable ink composition, for example, an ink jet recording apparatus described below can be used.

  FIG. 1 is a perspective view of an ink jet recording apparatus that can be used in the ink jet recording method according to the present embodiment.

  The ink jet recording apparatus 20 shown in FIG. 1 has a motor 30 for feeding the recording medium P in the sub-scanning direction SS, a platen 40, and a radiation curable ink composition having a small particle size and ejected from the head nozzle to record the recording medium P. A print head 52 serving as a recording head for discharging the ink, a carriage 50 mounted with the print head 52, a carriage motor 60 for moving the carriage 50 in the main scanning direction MS, and a radiation curable ink composition are discharged by the print head 52. And a pair of actinic radiation irradiating devices 90A and 90B for irradiating the ink adhering surface on the recording medium P with actinic radiation.

  The carriage 50 is pulled by a pulling belt 62 driven by a carriage motor 60 and moves along a guide rail 64.

  The print head 52 shown in FIG. 1 is a serial head for full color printing that ejects ink of three or more colors, and is provided with a large number of head nozzles for each color. In addition to the print head 52, the carriage 50 on which the print head 52 is mounted is supplied to the print head 52 and a black cartridge 54 as a black ink container that contains black ink supplied to the print head 52. A color ink cartridge 56 is mounted as color ink containing color ink. The ink contained in each cartridge 54 and 56 is the radiation curable ink composition described above.

  A capping device 80 for sealing the nozzle surface of the print head 52 when stopped is provided at the home position of the carriage 50 (the position on the right side in FIG. 1). When the print job ends and the carriage 50 reaches above the capping device 80, the capping device 80 is automatically raised by a mechanism (not shown) to seal the nozzle surface of the print head 52. This capping prevents the ink in the nozzles from drying out. The positioning control of the carriage 50 is performed to accurately position the carriage 50 at the position of the capping device 80, for example.

  By using such an ink jet recording apparatus 20, a radiation curable ink composition can be discharged onto a recording medium. In addition, according to the inkjet recording apparatus 20, the process (a) and the process (b) can be continuously performed by one apparatus without performing the process (a) and the process (b) by separate apparatuses. It becomes possible.

2.2. Step (b)
This step is a step of irradiating the discharged radiation curable ink composition with actinic radiation having an emission peak wavelength in a range of 350 nm to 400 nm from an actinic radiation light source. According to this step, the radiation curable ink composition ejected on the recording medium is irradiated with actinic radiation having a specific wavelength, whereby the radiation curable ink composition is cured and an image is recorded on the recording medium. can do.

  Hereinafter, the case where a process (b) is performed using the inkjet recording device 20 mentioned above is demonstrated in detail.

  2 is a front view of the active radiation irradiation apparatus 90A (corresponding to 190A in FIG. 2) and 90B (corresponding to 190B in FIG. 2) shown in FIG. FIG. 3 is an AA arrow view of FIG.

  As shown in FIGS. 1 to 3, the actinic radiation irradiation apparatuses 190 </ b> A and 190 </ b> B are respectively attached to both side ends along the moving direction of the carriage 50.

  As shown in FIG. 2, the actinic radiation irradiating apparatus 190A attached on the left side of the print head 52 is placed on the recording medium P during the right scanning when the carriage 50 moves in the right direction (arrow B direction in FIG. 2). Actinic radiation irradiation is performed on the ejected ink layer 196. On the other hand, the actinic radiation irradiation device 190B attached on the right side of the print head 52 has an ink layer ejected onto the recording medium P during left scanning when the carriage 50 moves leftward (in the direction of arrow C in FIG. 2). 196 is irradiated with actinic radiation.

  Each of the actinic radiation irradiation apparatuses 190A and 190B is attached to the carriage 50, and controls the light emission and extinction of the actinic radiation light source 192 (not shown), and a housing 194 in which the actinic radiation light sources 192 are aligned and supported one by one. And a control circuit. As shown in FIGS. 2 and 3, each of the actinic radiation irradiation apparatuses 190A and 190B is provided with one actinic radiation light source 192, but two or more actinic radiation light sources 192 may be provided. As the active radiation light source 192, it is preferable to use either an LED or an LD. Thereby, compared with the case where a mercury lamp lamp, a metal halide lamp, and other lamps are used as the active radiation light source, it is possible to avoid an increase in the size of the active radiation light source due to equipment such as a filter. Further, the intensity of the active radiation emitted by absorption by the filter does not decrease, and the radiation curable ink composition can be efficiently cured.

In addition, each of the actinic radiation light sources 192 may have the same wavelength or different wavelengths. When an LED or LD is used as the actinic radiation light source 192, the emission peak wavelength of the emitted actinic radiation may be in the range of about 350 to 400 nm.

  According to the actinic radiation irradiation apparatuses 190A and 190B described above, recording in the vicinity of the print head 52 is performed on the ink layer 196 deposited on the recording medium P by ejection from the print head 52, as shown in FIG. The actinic radiation 192a is irradiated by the actinic radiation light source 192 that irradiates the medium P, and the surface and the inside of the ink layer 196 can be cured.

The irradiation amount of the actinic radiation varies depending on the thickness of the ink layer 196 deposited on the recording medium P, and thus cannot be strictly specified. Although preferable conditions are appropriately selected, the radiation curable ink composition described above is used. Can be sufficiently cured with an ultraviolet irradiation amount of about 300 to 1000 mJ / cm ² .

  According to the ink jet recording apparatus 20, a plurality of radiation curable ink compositions ejected onto the recording medium P even during full color printing in which the radiation curable ink composition has a low viscosity and the ink layer has a relatively thin film thickness. Can be cured well without causing problems such as bleeding or color mixing.

  The configuration of the inkjet recording apparatus 20 is not limited to the configuration of the recording head, the carriage, the actinic radiation light source, and the like described above, and various modes are adopted based on the purpose of the inkjet recording method according to the present embodiment. can do.

3. Recorded matter A recorded matter according to an embodiment of the present invention is recorded by the ink jet recording method described above. Since the image recorded on the recording medium is formed using the radiation curable ink composition described above, it is excellent in flexibility and excellent in abrasion resistance and adhesion to the recording medium. .

  The use of the recorded matter according to the present embodiment is not particularly limited, and can be used as an image recorded on the recording medium described above. The image recorded on the recording medium is excellent in flexibility, and also excellent in abrasion resistance and adhesion to the recording medium. Is suitable.

4). Examples Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.

4.1. Preparation of Pigment Dispersion Cyan Pigment (made by Ciba Japan Co., Ltd., trade name “IRGALITE BLUE GLVO”) 15 parts by weight as a colorant, Solsperse 36000 (manufactured by LUBRIZOL) 1.2 parts by weight as a monofunctional monomer Phenoxyethyl acrylate (Osaka Organic Chemical Co., Ltd., trade name “V # 192”) was added to make 100 parts by mass, and the mixture was stirred to obtain a mixture. This mixture was subjected to a dispersion treatment for 6 hours together with zirconia beads (diameter 1.5 mm) using a sand mill (manufactured by Yaskawa Seisakusho Co., Ltd.). Then, the cyan pigment dispersion liquid was obtained by isolate | separating a zirconia bead with a separator.

  In Comparative Example 1, a cyan pigment dispersion was obtained by using dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name “FA512AS”) instead of the phenoxyethyl acrylate.

4.2. Preparation of radiation curable ink composition After mixing and completely dissolving the reaction components, photopolymerization initiator, slip agent and polymerization inhibitor so as to have the composition (% by mass) described in Table 1 or Table 2, The cyan pigment dispersion was added dropwise thereto while stirring so that the concentration of the cyan pigment would be the concentration shown in Table 1 or Table 2. After completion of dropping, the mixture was stirred for 1 hour at room temperature, and further filtered through a 5 μm membrane filter to obtain each radiation curable ink composition.

In addition, the component used in the table | surface is as follows.
・ Phenoxyacrylate (Osaka Organic Chemical Industry Co., Ltd., trade name “V # 192”)
・ Dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name “FA512AS”)
・ Dicyclopentenyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name “FA511AS”)
・ N-Vinylcaprolactam (trade name “N-Vinylcaprolactam” manufactured by BASF)
・ Dimethylol tricyclodecane diacrylate (Daicel Cytec Co., Ltd., trade name “EBECRYL IRR214K”)
Amino acrylate (Daicel Cytec Co., Ltd., trade name “EBECRYL 7100”)
IRGACURE 819 (Ciba Japan Co., Ltd., bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, photopolymerization initiator)
DAROCUR TPO (Ciba Japan Co., Ltd., 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, photopolymerization initiator)
・ DETX (Nippon Kayaku Co., Ltd., photopolymerization initiator)
IRGACURE 184 (Ciba Japan Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone, radical photopolymerization initiator)
-BYK-UV3500 (by Big Chemie Japan Co., Ltd., polydimethylsiloxane having a polyether-modified acrylic group, slip agent)
・ P-Methoxyphenol (manufactured by Kanto Chemical Co., Ltd., polymerization inhibitor)
・ IRGALITE BLUE GLVO (Ciba Japan Co., Ltd., cyan pigment)
・ Solsperse 36000 (manufactured by LUBRIZOL, dispersant)

4.3. Preparation of Recorded Material Using an ink jet printer PX-G5000 (manufactured by Seiko Epson Corporation), the radiation curable ink composition was filled in each nozzle row. A solid pattern image is printed on a PVC film or PET film at normal temperature and normal pressure so that the dot diameter of the ink is medium and the film thickness of the printed material is 10 μm, and in the ultraviolet irradiation device mounted on the side of the carriage. A solid pattern image was cured by irradiating ultraviolet rays having two wavelengths of 365 nm and 395 nm with irradiation intensity of 60 mW / cm ² from the UV-LED. As described above, a recorded matter in which a solid pattern image was printed on a PVC film or a PET film was produced. The curing process was performed under curing conditions such that the integrated light amount was 400 mJ / cm ² .

4.4. Evaluation Test The following evaluation test was performed on the obtained recorded matter. The following evaluation tests were all performed in a room temperature environment.

4.4.1. Evaluation of Curability As described above, a solid pattern image was printed on a PET film, and a curing process was performed using UV-LED under curing conditions such that the integrated light amount was 400 mJ / cm ² . The surface of the obtained printed matter was rubbed with a cotton swab to evaluate the image curability. The classification of evaluation criteria is as follows.
A: No scratches on the surface and deep part of the printed material.
B: Insufficient curing of the surface and deep part of the printed matter and scratches.

4.4.2. Evaluation of flexibility First, the recorded matter was cut into a predetermined size (the length at this time is L ₀ ), and set in a tensile tester (manufactured by A & D Corporation). The tensile speed of the tensile tester was set to 100 mm / min, and the recorded matter was pulled by the tensile tester, and the time when the recorded matter was cracked or peeled (hereinafter referred to as “crack etc.”) was visually confirmed. . The length of the recorded material that was pulled was calculated from the time from the start of pulling to the time when a crack or the like was generated. The elongation (%) of cracks and the like of the image formed on the PVC film or PET film was calculated from the following formula (1), and the flexibility of the recorded matter was evaluated.

Crack elongation of image, etc. (%) = {(L−L ₀ ) / L ₀ } × 100 (1)
The classification of evaluation criteria is as follows.
AAA: The elongation is 180% or more.
AA: The elongation is 160% or more and less than 180%.
A: The elongation is 140% or more and less than 160%.
B: The elongation is 120% or more and less than 140%.
C: The elongation is 100% or more and less than 120%.
D: The elongation is less than 100%.

4.4.3. Evaluation of adhesion According to JIS K5600-5-6 (General coating test method-Part 5: Mechanical properties of coating film-Section 6: Adhesion (cross-cut method)) and PVC film or PET film and image The adhesion was evaluated. The classification of evaluation criteria is as follows.
0: The edge of the cut is completely smooth and there is no peeling in the eyes of any lattice.
1: Small peeling of the coating film is observed at the intersection of cuts.
2: The coating film is peeled along the edge of the cut and / or at the intersection.
3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eye are partially or completely peeled off.
4: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off.
5: The degree of peeling exceeds Category 4.

4.4.4. Evaluation of abrasion resistance According to JIS K5600-5-10 (Paint General Test Method-Part 5: Mechanical Properties of Coating Film-Section 10: Abrasion Resistance (Test Piece Reciprocation Method)) The rubbing resistance of the image formed on the PET film was evaluated. The classification of evaluation criteria is as follows.
1: The surface of the image is not scratched at all.
2: The surface of the image has less than 5 scratches.
3: The surface of the image has 5 to 10 scratches.
4: Half of the surface of the image is scratched.
5: The entire surface of the image is scratched.

4.4.5. Evaluation of Storage Stability The radiation curable ink composition was placed in a sample bottle and completely sealed. The sample bottle was stored at 60 ° C. for 1 week, and then the viscosity when returned to 20 ° C. was measured. The storage stability was evaluated by comparing the viscosity at 20 ° C. before storage with the viscosity at 20 ° C. after storage. The viscosity was measured with a viscoelasticity tester MCR-300 (manufactured by Pysica) after placing the sample bottle in a constant temperature bath at 20 ° C. for 1 hour. The classification of evaluation criteria is as follows.
A: The change in viscosity is less than 1 mPa · s.
B: The viscosity increased or decreased from 1 mPa · s to less than 5 mPa · s.
C: The viscosity increased or decreased by 5 mPa · s or more.

4.5. Evaluation results The results of the above evaluation tests are also shown in Tables 1 and 2.

  According to the radiation curable ink compositions of Examples 1 to 8 shown in Table 1, all have good storage stability, and since the elongation such as cracks is 100% or more, they are rich in flexibility. Further, an image having good adhesion to the PVC film and the PET film and excellent in abrasion resistance and curability could be recorded on the PVC film or the PET film.

  In the radiation curable ink compositions of Reference Examples 1 and 2 shown in Table 1, the component (F) in the reaction component of Example 1 was changed to another structure, but the component (F) Images with slightly lower curability than the other examples were recorded due to the difference in combination. However, the evaluation results of the recorded matter after curing were good.

  On the other hand, since the radiation curable ink composition of Comparative Example 1 in Table 2 does not contain the components (A), (B) and (C) in the reaction component, the adhesion to the PVC film and the PET film. Was recorded, and the image was not excellent in abrasion resistance.

  Since the radiation curable ink composition of Comparative Example 2 in Table 2 does not contain the component (A) and the component (B) in the reaction component, the adhesion to the PVC film and the PET film is insufficient, and An image having no excellent abrasion resistance was recorded.

  The radiation curable ink composition of Comparative Example 3 in Table 2 loses balance because the content of the component (A) in the reaction component is less than 5% by mass, and has poor adhesion to the PVC film and the PET film. An image that was sufficient and not excellent in abrasion resistance was recorded. However, the radiation curable ink composition of Comparative Example 3 gave better results in terms of adhesion and scratch resistance than the radiation curable ink compositions of Comparative Example 1 and Comparative Example 2.

  The radiation curable ink composition of Comparative Example 4 in Table 2 loses balance because the content of the component (A) in the reaction component exceeds 15% by mass, and is left in an environment of 60 ° C. for 1 week. As a result, thickening was confirmed.

  Since the radiation curable ink compositions of Comparative Example 5 and Comparative Example 6 in Table 2 did not contain the component (B) in the reaction component, an image having no excellent abrasion resistance was recorded.

  In the radiation curable ink composition of Comparative Example 7 in Table 2, since the content of the component (B) in the reaction component was less than 1% by mass, an image having no excellent abrasion resistance was recorded.

  The radiation curable ink composition of Comparative Example 8 in Table 2 loses balance because the content of the component (B) in the reaction component exceeds 20% by mass, and the occurrence elongation of cracks and the like is less than 70%. The image was not excellent in flexibility at all, but an image excellent in abrasion resistance was recorded.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 20 ... Inkjet recording device 30 ... Motor, 40 ... Platen, 50 ... Carriage, 52 ... Print head (recording head), 54 ... Black ink cartridge, 56 ... Color ink cartridge, 60 ... Carriage motor, 62 ... Traction belt, 64 ... guide rail, 80 ... capping device, 90A (190A), 90B (190B) ... active radiation irradiation device, 192 ... active radiation light source, 194 ... housing, 196 ... ink layer, P ... recording medium

Claims (7)

(A) 5 to 15% by mass of N-vinylcaprolactam in the reaction component;
(B) a polyfunctional acrylate having an alicyclic structure of 1% by mass to 20% by mass in the reaction component;
(C) phenoxyethyl acrylate,
(D) a monofunctional acrylate having an alicyclic structure;
(F) a photopolymerization initiator;
A radiation curable ink composition comprising: In claim 1,
The radiation-curable ink composition, wherein the polyfunctional acrylate (B) having an alicyclic structure is dimethylol tricyclodecane diacrylate. In claim 1 or claim 2,
A radiation-curable ink composition comprising (D) a monofunctional acrylate having an alicyclic structure in a reaction component of 35% by mass to 65% by mass. In any one of Claims 1 to 3,
The (D) monofunctional acrylate having an alicyclic structure is at least one selected from dicyclopentenyl acrylate, dicyclopentanyl acrylate, and dicyclopentenyloxyethyl acrylate. In any one of Claims 1 thru | or 4,
Furthermore, (E) a radiation curable ink composition containing aminoacrylate. In any one of Claims 1 thru | or 5,
A radiation-curable ink composition having a viscosity at a measurement temperature of 20 ° C. of 10 mPa · s to 40 mPa · s and a surface tension at a measurement temperature of 20 ° C. of 20 mN / m to 30 mN / m. (A) a step of discharging the radiation curable ink composition according to any one of claims 1 to 6 onto a recording medium;
(B) irradiating the discharged radiation curable ink composition with actinic radiation having an emission peak wavelength in a range of 350 nm to 400 nm from an actinic radiation source;
An ink jet recording method comprising:

Images